Copperable disazo dyestuffs



United States Patent 2,835,663 COPPERABLE DrsAzo DYESTUFES Jakob Benz, Basel, Switzerland, assignor, by mesne assignments, to Saul & C0., Newark, N. J., as nominee'of Fidelity Union Trust (Iompany, executive trustee under Sandoz Trust No Drawing. Application May 19, 1955 Serial No. 509,673

Claims priority, application Switzerland May 21, 1954 6 Claims. (Cl. 260-153) The present invention relates to new copperable disazo dyestuffs and their preparation. 7

It has been found that new copperable disazo dyestulrs are obtained when 1 mole of a six -membered triazine compound containing not more than three replaceable halogen atoms attached to carbon atoms, 2 moles of a naphthalene derivative having the general formula:

where n denotes the number 1 or 2, 1 mole of a diazotised 2-amino-l-hydroxybenzene which contains attached to the nucleus an alkylsulfonyl group or a sulfonic acid amide group which may be further substituted on the nitrogen atom, and 1 mole of a diazotised 2-amino-lhydroxybenzene which may carry further substituents commonly present in azo dyestuffs, are allowed to react upon each other in such a way that the primary amino groups of'the 2 moles of the naphthalene derivative of general Formula I are transferred to 2 carbon atoms of the triazine compound with removal of hydrogen halide, while the 2 moles of the diaz otised Z-amino-l -hydroxybenzenes each react with the 6 -position of the 2 moles of the naphthalene derivative of general Formula I; should a third replaceable halogen atom be present on the triazine ring of the resulting disazo dyestuft it may be replaced by a hydroxyl group or a primary, secondary or tertiary amino group by treatmentwith alkali, ammonia or a primary or secondary amine.

Valuable mixtures of disazo dyestuffs according to this invention are obtained when 2 moles of a mixture in any desired proportions of two or more different naphthalene derivatives of general Formula I are employed in place of the 2 moles of a naphthalene derivative of general Formula I.

Depending on the method of preparation employed, the new copperable disazo dyestuffs may be obtained as homogeneous products or as mixtures of different components, all of which however correspond to the general formula:

HOaS- wherein x stands for halogen, the hydroxy group or a primary, secondary or tertiary amino group,w stands for a lower alkylsulfonyl group, the sulfonic acid amide group or a sulfonic acid amide group, the nitrogen atom of which may be substituted by lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, arylalkyl or aryl groups, HOR stands for substituted residue of a hydroxyben- Patented May 20, 1958 "lce and R-OH represent the radicals of 2-amino-l-hydroxy 4-methylsulfonylbenzene, 2-amino-1hydroxybenzenelsulfonic acid amide or 2amino-l-hydroxybenzene-4-sulfonic acid methylamide, x the radical of the aminobenzene derivative, and m and n the number 1.

The dyestuffs, in the form of their water-soluble alkaline salts, are dark-colored powders characterised by very high aflinity for vegetable fibers. Their coppered dyeings on cotton and regenerated cellulosic fibers are a clearbluish red in shade and possess very good fastness to light and washing. The coppering process can be carried out by the customary single-bath or aftercoppering methods. Uncoppered dyeings may also be treated with cationicpossibly basic-complex copper compounds, e. g. the polyalkylene polyamines which contain copper in complex combination; such aftertreatmcnt imparts excellent fastness properties, notably fastness to light, washing, water and perspiration.

The Z-amino-l-hydroxybenzenes used as starting materials for the new disazo dyestuffs contain according to this invention an alkylsulfonyl group attached to the nucleus or a sulfonic acid amide group, the nitrogen atom of which may be further substituted. Compounds of this type are the Z-amino-1hydroxy-4alkylsulfonylbenzenes, e. g. Z-amino-1hy-droxy-4-methylsulfonylbenzene and 2-amino-l-hydroxybenzene-4- or -5 or 6-sulfonic acid amides. Besides the substituents specified for this invention, the Z-amino-l-hydroxybenzenes may also carry further nuclear substituents, e. g. halogen atoms or alkyl groups, and the sulfonic acid amides may be further substituted in the amine radical. Special mention may be made of the sulfonic acid methylamides, ethylamides, (2-hydroXy)-ethylamides, (3-methoxy)- propylamides, cyclohexylamides, benzylamides and phenylamides.

Among the other Z-amino-l-hydroxybenzenes used to produce the new disazo dyestuffs and which may carry further substituents commonly present in the azo dye stuifs, the following may be enumerated: the Z-aminc-lhydroxybenzenes which are substituted by sulfonic acid, nitro, alkyl, acylamino, alkylsulfonyl or sulfonic acid amide groups, the latter of which may be substituted on the nitrogen atom, and/or halogen atoms.

Examples of triazine compounds are cyanuric bromide.

derivative of general Formula I or 2 moles of a mixture condensation product of 1 mole of cyanuric chloride, 2 in any desired proportions of two or more different commoles of Z-amino-S-hydroxynaphthalene-7-sulfonic acid pounds of this type may be condensed with 1 mole of and 1 mole of aminobenzene. To accelerate coupling, the triazine compound. The condensation of the naph- -10 vol. percent pyridine or 'a technical mixture of pyri thalene derivatives of general FormulaI with the triazine 5 dine bases is added to the mass. On completion of compound is carried out preferably in'an aqueous mecoupling the disazo dyestuff so formed is salted out, dium and in the presence of an acid-binding agent. The filtered OE and dried. It corresponds to the formula HO IIIH-CQHGE N SOT-CH3 SOz-CH; resulting intermediate compound is coupled with 1 mole and is a dark-coloured powder which dissolves in water each of a diazotised Z-amino-l-hydroxybenzene conformof Weakly alkaline reaction to give a violet-coloured ing to the above definition or with 2 moles of a mixture solution. From such a solution the dyestuft has very in any desired proportions of two or more different diazo high afl'mity for cotton and regenerated cellulosic fibers. compounds of this type. Coupling is best carried out On subsequent treatment with copper compounds by esin an alkaline medium and the reaction can be accelerated 0 tablished methods, the dyeings display clear bluish red by an addition of tertiary organic bases, e. g. pyridine, shades having very good fastness to washing and perspirquinoline or a technical mixture of pyridine bases. ation and excellent light fastness.

In the resulting disazo dyestuffs a third replaceable halogen atom which may be present on the triazine ring can be replaced by a hydroxyl group or a Primary, f To a neutral solution at 0-3 of 23.9 parts of 2- ondary P tertiary amino group y e action alkall, amino-S-hydroxynaphthalene-7-sulfonic acid in 400 parts ammonla a P Y or Secondary amlneof water is added in the course of minutes a dispersion Another y In Whleh the Process can be Performed of 18.4 parts of finely powdered cyanuric chloride in 500 Consists in coupling 1 mole each of a diaZOfiSed 2-amil10- parts of ice water. Diluted sodium carbonate solution is Example 2 l-hydfoxybefllene conforming the above definition 0f 30 added dropwise to keep the reaction product weakly acid. 2 moles of a mixture in any desired proportions of two The suspension is agitated for afurther hour at 0-3, or more different diazo compounds of this type with 2 then heated to 25, at which temperature a weakly moles of a naphthalene derivative of general Formula I alkaline solution of 35.8 parts of 2-(4'-amino)-benzoylor with 2 moles of a mixture in any desired proportions 3 a ino-5-hydroxynaphthalene-7-sulfonic acid in 400 parts of two or more diiferent naphthalene derivatives of this Of Water is added. The mass is stirred for 3 hours at type, and reacting the 2 moles of the aminomonoazo -45, during which time it is fed With a SOlllilOll Of compound with 1 mole of a triazine compound according Parts of Sodium Carbonate in 500 Parts Of Waterto the invention. Here also coupling is etfectedto best Finallylg Parts of aminobenzene are P into the advantage i an lk i medium, so that the diazo 40 condensation mass, which is then heated for 2 hours at groups react with the 6-position of the naphthalene de- Following this Parts of concentrated hydro rivatives f general Formula I chlorrc acid are added. The ternary condensation prod- A third method of application of the process, which not thus formed is salted out of the condensation soluis suitable for producing those disazo dyestuffsof genand fi eral Formula II in which it and/or m denote the num- A'pomon of the molst. filter'vcake i to her 2 consists in linking the diazo compound named in parts of the dry condensation product is dissolved in 400 the preceding paragraph with a 2-(4-nit ro)-benzoylparts 9 water i an .additlon of 15 Pints of sodlllm amino 5 hydmxy naphthalene 7 sulfonic acid which y carbonate. To this solution is added the diazo suspension carry further substituents on the benzene nucleus, and emailed as described In Examp 1e 1 from parts of reducing the nitro group in the resulting nitromonoazo 0 Zammo1'hYdIOXYA'methYlsulfonYlbenzene' To accel' compound to an ammo g o p e am n az y rate coupllng, an addition of pyrldrne or a mixture of 'dine bases is made. The mass i a t t d til Stuff thu f m d pyrr s g1 a e un cou S or e 13 reacted Wlth the mazme Compound pling 1s completed, when the resulting disazo dyestulf is by the second method of application of the process salt t ed out, filtered 01f a d d In the second and third methods of application also a formula n med It Corresponds to the on on l rr-oam OH OH =N V I E/ T N=N HO s- NH a N o NHQCO-NH SOaH S02 CH3 SIOZCH3 halogen atom which may be present in the triazine ring ppered dyeings of the dyestutf on cotton and regenean be p e y one offhe above-nemed 1 erated cellulosic fibers are bluish red in shade and possess following eXamples Illustrate the lIlVeIltlOll Without outstanding fastness to washing and good fastness to limiting 1ts scope. All parts and percentages are by li h welght; temperatures are in degrees centigrade. Example 3 6 9.2 parts of 2-amino1-hydroxy-4-methylsulfonyl- 18.7 parts of 2-amino-1-hydroxy-4-methylsulfonylbenzene are diazotised as described in Example 1. The

benzene are dissolved with 15 parts of concentrated hydiazo solution is run into a solution I h I of 31.3 arts of the dro chlorrc acid in 200 parts of water anddlazotised at ternary condensation product of 1 mole 3f cyanuric 10 with 6.9 parts of sod um nitrite. The-resulting sus+ chloride, 2 moles of 2-amino-5-hydroxynaphthalene-7- pension 1s runlnto a solutronof 350 parts of water, 15 sulfonic acid, 1 mole of aminobenzene, and 15 parts of parts of sodium carbonate and 31.3 parts of the ternary sodium carbonate in 350 parts of water. The coupling mixture is agitated until the diazo compound is no longer indicated. Then an aqueous solution of the diazo compound obtained in the usual Way fromlO parts "o'f2-" filtered oif. By-products are eliminated by re-dissolving in hot water and thedyestuif then dried. It corresponds 20 to the formula Hons don-C and possesses similar properties to the disazo dyestuif described in Example 1.

Example 4 9.2 parts of Z-amino-1-hydroxy-4-methylsulfonylbenzene are diazotised in the normal way and the diazo solution run into a solution of 31.3 parts of the ternary condensation product of 1 mole of cyanuric chloride,i2 moles of 2-amino-5-hydroxynaphthalene-7-sulfonic acid,

1 mole of aminobenzene and 15 parts of sodium carbonate in 250 parts of water. The coupling mixture is agitated until the diazo compound is no longer indicated.

'tion filtered. The'dyestuif corresponds to the formula Oar-CH5 35 directions given in the foregoing examples.

6 tained in the usual manner from 7.2 parts of 2-amino-1- hydroxy-4-chl0robenzene is added to the mixture, fol- 1owe'd'byS-=I0"'Vol;'percent'of'pyridine or a technical" mixture of pyridine bases to accelerate coupling. When coupling is completed the resulting diazo dyestutf is pre cipitated from the coupling mixture by an addition of sodium chloride and then filtered off. It is freed of byproducts by redissolving in hot Water and the purified soluv NH-CuHu OH SOaH 'and" is a dark-coloured powder giving violet-coloured aqueous solutions of weakly alkaline reaction. It hasvery good aifinity forcotton and regenerated cellulosic fibers. Aftercop'pered dyeings on these fibers are bluish red in shade and show very good fastness to washing and perspiration and; excellent fastness to light.

The following table lists other copperable disazo dyestuifs which can be obtained in accordance with the They correspond to the general Formula II and are characterised by. the diazo components (A) and (B) employed as starting materials for the dyestuffs of-general Formula II (columns II and III), the substituent x (column IV) by the values m and n .(col umns V and VI) and the shade Then an aqueous solution of the diazo compound ob- 40 of the aftercoppered dyeing on cotton (column VII).

I II III IV V VI VII Shade of Example 1 the after- No. Diazo Component (A) Diazo Component (B) 2? 1n= n= coppered dyeing on cotton 5 2-amln0-1-hydroxy-4-methylsulfo- 2-amino-1-hydroxy-4-methyisu1iophenylamino 2 2 rubine.

nylbenzene. .nylbenzene. 6 2-amiuo-1-hydroxy-4-cthylsn1fo- 2-ammo-l-hydroxy-4-ethylsultodo 1 1 Do.

nylbenzene. nylbenzene. 7 2-ammo-1-hydr0xybenzene-4-sul-', 2-amino-1-hydroxybenzene-4-suldo 1 1 Do,

ionic acid methylamide. ionic acld methylamide. 8 2-amino-1-hydroxybenzene-4-sul- 2amino-1-hydroxybenzene-4-su1- do 1 1 Do.

ionic acid (3-methoxy)-propyliiomc acid I(3-methoxy)-propyiamide. am e. 9 2-amino-1-hydroxybenzcne-4-su1- Z-amino-i-hydrorrybenzene-4-sui- ....-do 1 1 Do.

ionic acid amide. ionic acid amide. i 10 2-amino-l-hydroxy-4-methy1sulfo- 2-amino-1-hydroxybenzene-4-su1- do 1 1 Do. nylbenzene. fgnic acid (2-hydroxy)-ethylamv e. 11 rln 2-amino-1-hydroxybenzene-4-suldo 1 1 Do.

' r fonic acid phenyiamide. 12 do cyclohexyla- 1 1 Do. i V V mine.

1's dn 2-am ino-1-hydroxybenzene-4-sulphenylamino.. 1 2 D0. ionic acid methylamide.

14 2-amino-l-hydroxyi-ethylsnlfo- 2-ami.no-1-hydroxybenzene-4-suido 1 1 Do.

- nylbenzene. ionic acid amide. 15 do -fl amino 1 1 D0. 16 2-amino-l-hydroxy-4-methylsul- Z-amino-1-hydroxy-4-nitrobenzene phenylaminm. 1 1 Do.

ionylbenzene. I 17 do do hydroxy 1 1 Do. 18 2-ammo-1-hydroxybenzene-4-su1- 2-amino-l-hydroxy-S-chlorbenphenylaminm. 1 1 Bordeaux. ionic acid methyiamide. zene-4-suiion1c acid.

19 2-amino-1-hydroxy-4-methyisul- 2amino-1-hydr0xybenzene-4-cardo 1 1 rubine.

fonylbenzene. boxylic acid phenylamide. 20 2-amino-1-hydroxy-4-ethy1su1fo- Z-amino-l-hydroxyi-nltrobenzened0 1 1 Do. nylbenzene. 21 rin dn ohlnrme 1 1 D0 22 2-amino-1-hydroxybenzene-4-sui- 2amino-1-hydroxy-4-chiorbenzene do 1 1 Bordeaux.

ionic acid amide. 23 do methylaminou 1 1 Do. 24 Z-amino-1-hydroxybenzene-4-suldo phenylaminm- 1 1 Do.

I 1'fonic'acidmethylamida. W 25 hydroiryethyl- 1 1 Do.

amino.

I II III [IV V VI VII 7 Shade of Example 7 the after- No. Diazo Component (A) Diazo Component (B) z= n: n= eoppered dyeing on cotton Z-amlno-l-hydroxy-4-methylsulphenylamino.. 1 1 Do.

fonylbenzene. 2-am1no-1-hydroxybenzene-4-suido .do 1 1 Do.

fonlc acid methylamlde. or V V 2-amino-l-hydroxy-dl-znethylsui- .do 1 1 Do.

fonylbenzene. do 2.-a mino-i-hydroxy-G-chlorbendo 2 2 Do.

s zene-l-sulfonicacid. 30 "do 2-amino-1-hydroxybenzene-4-sul- .do 1 2 rublne.

ionic acid amide. 31 2-arnino-l-hydroiybenzene--sul- 2-amino-1-hydroxy-4-methylben- 1 1 Do.

ionic acid amide. zone. 32 2-amino-1-i1ydroxybonzene-4-sul- 2-amino-l-hydroxy-G-chlorben- 1 1 Bordeaux. 7

ionic acid phenylamide. zene-4-sulfonic acid. 7 33 2-amino-1rl1ydroxybenzeno-4-su1- do.... 1 1 Do.

fonic acid cyclohexylamide. 34 2-amino-l-hydroxybenzene-4-suldo 1 1 Do.

ionic acid benzylamide. r 35 ZamIgm-1-hydroxy-4-ethylsulfo- 2-amino-1-hydroxy-4-nitrobenzene. 1 2 rulpine.

ny enzene. V 36 2-amino-1-hydroxy-4-methylsuldo 4-methoxyphen- 1 1 Do.

ionylbenzene. ylamino. 37 -do ..do methylphenyl- 1 1 Do.

- amino. v 38 Z-amino-1-hydroxybenzene-4-suido phenylamino- 1 1 'Do.

Representative examples are 7, 26 and 27. The formulae of the thus-obtained dyestufls are: squeezed.

Example 7 OH OH IIIHCQHI OH OH N=N N:

in? N nols- NH-C\ (Lim- -soln EJO1-NH-CHI v SOr-NH-CHi 7 Example 26 on GR lTIH-OuE OH OH 0 N=N- -N=N N N H0;S- Nil-l d-NH 50111 N sol-0H; 1

Example 27 OH OH NH-CeHs OH OH N=N 7 N==N 01 N N HOaS NH-PJ J7-NH BOaH t 02-NH-CH: 7 01 Example 39 100 parts of cotton fabric, thoroughly wetted out, are. entered into a dyebath at 30 containing 3000 parts of- 0' water, 0.7 part of anhydrous sodium carbonate, 0.7 part of the concentrated dyestuff obtained according to Example l, and 10 parts of crystallised sodium sulfate. The dyebath is heated to 100 in 30 minutes, two portions each of 10 parts of crystallised sodium sulfate being added at 50 and 90. The cotton is dyed for 15 minutes i at the boil, then a further parts of crystallised sodium' sulfate are added and the dyebath cooled for minutes.

The cotton is removed, rinsed in running water and While 'still'moist the material is treated for minutes in-an aftercoppering bath at containing 3000 parts of water, 3 parts of crystallised copper sulfate and 3 parts of glacial acetic acid. Finally the cotton is rinsed and dried. It is dyed ina bluish red shade of very good fastness to washingand-perspiration and excellent fastness to light.

Having thus disclosed the invention what is claimed is:

l. The copp'erable disazo dyestulfs which correspond to the formula wherein x stands for a member selected from the group consisting of a chlorine atom, the hydroxy group and primary and secondary aliphatic and carbocyclic amine groups, y stands for a member selected from the group consisting of lower alkyl, amino, lower alkylamino, lower 5 hydroxyalkylamino, lower alkoxyalkylamino, cyclohexyl- HOaS- SO -CH! amino, benzylamino and arylamino groups of the benzene series, HOR stands for a substituted residue of a hydroxybenzene, the hydroxy group of which is in ortho- 25 position to the N:N-group and the substituents of SOz-NH-CH which being selected from the group consisting of a 35 chlorine atom, nitro, lower alkyl, mononuelear carboxylic acid aryl amide, sulfonic acid, lower alkylsulfonyl, sul- 02-CHa 10 acid lower hydroxyalkylamide, sulfonic acid lower alkoxyalkylamide, sulfonic acid cyclohexylamide, sulfonic acid benzylamide and sulfonic acid arylamide groups of the benzene series, and m and n each stands for one of the numerals 1 and 2.

2. The copperable disazo dyestulf which corresponds 3. The copperable disazo dyesuff which corresponds to the formula 4. The copperable disazo dyestutf which corresponds to the formula N=N- G1 5. The copperable disazo dyestuif which corresponds to the formula 6. The copperable disazo dyestutf which corresponds fonic acid amide, sulfonic acid lower alkylamide, sulfonic 45 to the formula OH OH NH- O 0H5 O H O H References Cited in the file of this patent UNITED STATES PATENTS 1,667,312 Fritzsche et a1. Apr. 24, 1928 2,460,618 Bernasconi Feb. 1, 1949 2,538,568 Kaiser et a1. Jan. 16, 1951 Wehrli et a1. Nov. 1-, 1955 

1. THE COPPERABLE DISAZO DYESTUFFS WHICH CORRESPOND TO THE FORMULA 